Water soluble salts of basic prod



Patented Aug. 31, 1937 UNITED STATES PATENT orrics WATER SOLUBLE SALTS OF BASIC PROD- UCTS, VIZ., F IDIIDOETHERS, IJVHDO- THIOETHERS; TIV ES THEREOF AM'IDINES, 0R DERIVA- Alfred Eckelmann and Ernst Koch, Frankforton-the-Main-Hochst, Germany,

assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 2, 1934, Serial No. 751,252; In Germany November 9,

"I Claims. (Cl. 260127) The present invention relates to water-soluble salts of basic products, viz. of imidoethers, imidothioethers, amidines or derivatives thereof and to fibrous materials treated with these products.

We have found that fibrous materials, such as textiles, paper or pasteboard, may be advantageously treated with the hitherto unknown water-soluble salts of imidoethers, imidothioethers and amidines obtainable by treating 0 nitrile-mixtures of at least 2 nitriles, one of which contains at least more than 6 carbon atoms, with compounds of the following general formula:

wherein R represents an aliphatic, aromaticor hydroaromatic radical and X stands for 0H, SH,

(R1 standing for hydrogen or alkyl) and an acid.

As nitrile-mixtures there may be used the mixtures obtainable from nitriles of pure acids, for

'5 instance, by mixing pure stearic nitrile with pure palmitic nitrile, pure acetic nitrile with sebacic nitrile or pure lauric nitrile with benzoic nitrile. There may also be used mixtures of nitriles prepared from technical acid mixtures such as, for

:0 instance, nitriles which have been been preparedin known manner from palm nut oil fatty acid, palm oil fatty acid, coconut oil fatty acid, soya bean oil fatty acid, cotton seed oil fatty acid, linseed oil fatty acid, technical stearic acid, tech- :5 nical fish-oil fatty acid, technical naphthenic acid, technical montanic acid or resin acid, furthermore, nitrile-mixtures prepared from the carboxylic or dicarboxylic acids obtained by the oxidation of paraffin by means of air. The esters ioof the said technical fatty acid mixtures may likewise be used for the preparation of the nitriles.

As products of the above mentioned general formula R.X there may be mentioned, for in- !5 stance, methyl alcohol, ethyl alcohol, propyl alcohol,'butyl alcohol, amyl alcohol, octyl alcohol, do

decyl alcohol, octadecyl alcohol, glycol, glycerol, phenol, cresol, benzyl alcohol, cyclohexanol, furthermore, mercaptans such as, for instance,

methyl mercaptan, ethyl mercaptan or propyl merca'ptan and amines such as, for instance, monoethylamine, diethylamine and ethylenediamine.

As acids there may be used, for instance,

55 mineral acids such as hydrochloric acid or sulfuric acid, furthermore, organic acids, such as formic acid, acetic acid or oxalic acid.

As water-soluble salts of basic products there may be mentioned, for instance, mixtures of stearimidoethylether hydrochloride of the following constitution:

Nil C11H35-0 .HCl

Q-GzHa and laurimidobutylether-hydrochloride of the following constitution:

the imidoethylether hydrochloride of technical naphthenic acid, the imidobutylether formate of technical stearic acid, the amidine hydrochloride of palm nut oil fatty acid, the amidine formate of palm oil fatty acid.

Furthermore, there may be used the salts of imidoethers prepared from acid nitriles, mixtures of fatty alcohols and acid such as, for instance, the imidoether hydrochloride prepared from acetonitrile with technical stearyl alcohol and hydrochloric acid, furthermore the benzimidoether hydrochloride prepared from benzonitrlle with technical octyl alcohol, moreover, the

benzimidoether formate obtained from technical octadecyl alcohol and the acrylimidoether hydrochloride prepared from technical dodecyl alcohol.

All these substances have, besides a good dispersive power an excellent action as softening agent. By treating fibrous material such as textiles, paper or paste board, with solutions or emulsions of these substances;there are obtained r very good dressing and impregnating effects since the substances improve the sof feel of the fibers and render the material water-repellent and fast to creasing. According to their construction, the products are suitable for being used, for instance, as washing, wetting, levelling or dispersing agents, for rendering viscose artificial tissues fast to creasing, for waterprooflng'textiles and for delustering artificial silk.

5 The solubility and stability of the solutions of certain of the salts of these imidoethers, imidothioethers or amidines may be enhanced by using during the preparation or application of the solutions simultaneously emulsifying or dispersing agents or protective colloids. As-such assistants there may be mentioned for instance, the salts of urethanes carrying sulfo or carboxylic groups, fatty alcohol sulfonates, water-soluble oxethylated fatty alcohols, oxethylated fatty amines, oxethylated esters or amides of higher fatty acids, carbohydrates, oxethylated or other water-soluble albuminous products and similar water-soluble highly-molecular substances or mixtures of the said products. By the addition of the salts of 0 certain amidines the solubility and the stability of the solutions of the salts of imido-ethers may be enhanced.v

In some cases, for instance, in the preparation of dressings which are fast to washing and impregations which are fast to creasing it is advantageous to add buffering substances such as, hexamethylenetetramine in order to protect the fiber from being deteriorated. In other casesthe stability to washing of dressings or impregnations may be improved byworking in the presence of inorganic or organic ammonium salts.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight:

(1) 255 parts of a nitrile mixture prepared catalytically from technical stearic acid (containing about 55% of stearic acid, about 40% of palmitic acid and about 5% of oleic acid) and ammonia, are mixed with 46 parts of anhydrous 0 ethylalcohol, while stirring. Into this mixture there is introduced, first at C. and then at 15 C. and 10 C., respectively, hydrogen chloride until 46 parts thereof have been absorbed. Stirring is continued for some time until the product 5 solidifies.- The excess of hydrogen chloride may be removed according to one of the known methods. There are obtained about 220 parts of imidoethylether hydrochloride which dissolves very easily in water.

10 parts of this product are dissolved in a mixture of 620 parts of benzene and 240 parts of ethylalcohol and woolen yarn is impregnated with this solution at ordinary temperature. The yarn is then hydroextracted and dried. It has become excellently water-proof and is distinguished by a full soft feel.

(2) 200 parts of nitrile mixture prepared from coconut oil fatty acid (boiling at 100 C. to 200 C. under a mercury pressure of 12 mm., corresponding to about ,65% of laurylnitrile, about 21% of myristylnitrile, about 8% of palmitylnitrile and about 6% of stearyland. oleylnitrile) are mixed with 46 parts of anhydrous ethyl alcohol. Hydrogen chloride is then introduced at 5-10 C. until 42 parts thereof have been absorbed. In order to remove the excess of hydrochloric acid, dry air is conducted through the reaction mixture. There are obtained 280 parts of a product m which is easily soluble in cold water.

By impregnating at ordinary temperature viscose artificial silk yarn with a 20% solution of formaldehyde which contains 1 part of the above product per 100 parts of solution a product is 75 obtained which, after squeezing and drying at 100 C. is excellently fast to creasing and is, furthermore, distinguished by a soft feel.

(3) 32 parts of anhydrous methylalcohol are added to 195 parts of nitrile mixture prepared from palm nut oil fatty acid (boiling at 100 C. to 125 C. under a pressure of mercury of 2 mm., corresponding to about 68% of laurylnitrile and about 32% of myristylnitrile) and 38 parts of hydrogen chloride are introduced into the mixture of about 10 C. After standing for a prolonged time in the cold the reaction mass solidifies. Ether is introduced, while stirring, and cooling strongly whereupon the pure imidomethylether hydrochloride (215 parts) is obtained.

By dissolving 8 parts of this product and 10 parts of the reaction product of oleic acid chloride with methyl taurine sodium in 1 litre of a formaldehyde solution of strength and treating viscose artificial silk with this solution, there is obtained a tissue which after squeezing and drying at 110 C. is very fast to creasing.

(4) At about 0 C. to 5 C. 20 parts of hydrogen chloride are introduced into a solution of 133 parts of nitrile, obtainable from technical stearic acid, and 32 parts of ethyl mercaptan in 250 parts of ether, while stirring. Thereupon, the whole is stirred for some time. On standing for a prolonged time in the cold, the reaction product separates in such a quantity that the solution solidifies completely. It is filtered with suction, washed with ether and dried. 123 parts of imidoethylthioether hydrochloride, easily soluble in water, are thus obtained. The product is very suitable for being used as softening agent.

(5) 265 parts of nitrile, obtaining from technical stearic acid, are mixed with '73 parts of butylamine and 110 parts of HCl are introduced into this mixture. The whole 'is then treated for 3 to 5 hours at 120 C. to 130 C. and the reaction product is recrystallized from alcohol. An aqueous solution of 02% strength of this product shows in neutral or acid solution a good wetting action.

We claim:

1. Water-soluble mixtures of salts of basic compounds said mixtures being obtainable by causing a mixture of nitriles which is obtained by converting the acids contained in technical stearic acid into the corresponding nitriles, to react upon ethyl alcohol and hydrochloric acid.

2. Water-soluble mixtures of salts of basic compounds said mixtures being obtainable by causing a mixture of nitriles which is obtained by converting the acids contained in technical palm nut oil fatty acid into the corresponding nitriles, to react upon methyl alcohol and hydrochloric acid.

3. Water-soluble mixtures of salts of basic compounds said mixtures being obtainable by causing a mixture of nitriles which is obtained by converting the acids contained in technical stearic acid into the corresponding nitriles, to react upon butyl alcohol and hydrochloric acid.

4. Mixtures of salts of basic compounds containing at least one acid addition salt of the formula:

/NH RC/ .Acid XR,

wherein R means a member of the group consisting of aliphatic hydrocarbon radicals containing more-than 10 carbon atoms, aromatic, hydroaromatic and cycloaliphatic hydrocarbon radicals, X stands for a member of the group consisting of O and S, R1 means anali'phatic hydrocarbon radical, and at leastone acid addition salt of the formula:

R1 means an aliphatic hydrocarbon radical.

' 5. Mixtures of salts of imidoctherslcontaining at least one acid addition salt of the formula:

RC .Acid

wherein R means an aliphatic hydrocarbon radical containing more than 10 carbon atoms, R1 means an aliphatic hydrocarbon radical, and at least one acid addition salt of the formula:

R-C .Acid

cal, R1 means an aliphatic hydrocarbon radical.

6. Mixtures of salts of imidoethers containing an acid addition salt of the formula:

NH C11HuC .Acid

an acid addition salt of the formula:

/NH C1sH:uC .Acid

0-R and an acid addition salt of the formula:

NH CnHsa-O n O-Ri n W W V V in which formulae R1 stands for an aliphatic .Acid

- hydrocarbon radical.

7. Mixtures of salts of imidoethers containing an acid addition salt of the formula:

C11Hz3-C .Acid

and an acid addition salt of the formula:

C1;Hz7C .Acid

O-Ri in which formulae R1 stands for an aliphatic hydrocarbon radical.

ALFRED ECKELMANN.

ERNST KOCH. 

